Cobalt(III)‐Catalyzed C−H Activation: Counter Anion Triggered Desilylative Direct <i>ortho‐</i>Vinylation of Secondary Benzamides

Muniraj, Nachimuthu; Prabhu, Kandikere Ramaiah

doi:10.1002/adsc.201800649

Cited by 17 publications

(10 citation statements)

References 55 publications

(12 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[11j] Prabhu reported a Co(III)-catalyzed counter anion triggered desilylative direct ortho-vinylation of secondary benzamides furnishing the alkenylated product. [21] The above results indicated that alkynylsilane can participate in CÀ H activated coupling reaction and desilylative reaction simultaneously.…”

Section: Introductionmentioning

confidence: 76%

Cobalt‐Mediated Decarboxylative/Desilylative C−H Activation/Annulation Reaction: An Efficient Approach to Natural Alkaloids and New Structural Analogues

Chen

Lai

et al. 2022

Eur J Org Chem

View full text Add to dashboard Cite

show abstract

Section: Introductionmentioning

confidence: 76%

Cobalt‐Mediated Decarboxylative/Desilylative C−H Activation/Annulation Reaction: An Efficient Approach to Natural Alkaloids and New Structural Analogues

Chen

Lai

et al. 2022

Eur J Org Chem

View full text Add to dashboard Cite

show abstract

“…Organometallic cobalt species have merged as a promising type of catalysts for C−H bond functionalizations. For instance, [Cp*Co(CO)I 2 ] complex displayed modest activity as a pre‐catalyst with benzamide site‐selectivity for the vinylation of secondary benzanilides (Scheme ) . The same cobalt complex led to the same site‐selectivity for the intramolecular cyclization of alkynes (Scheme ) .…”

Section: C−c Bond‐forming Reactionsmentioning

confidence: 99%

Steering Site‐Selectivity in Transition Metal‐Catalyzed C−H Bond Functionalization: the Challenge of Benzanilides

Gramage‐Doria

2020

Chemistry A European J

View full text Add to dashboard Cite

SelectiveC ÀHb ond functionalization catalyzed by metal complexes have completely revolutionized the wayi n which chemical synthesis is conceived nowadays. Typically, the reactivityo fat ransitionm etal catalyst is the key to control the site-, regio-and/or stereo-selectivity of aC ÀHb ond functionalization. Of particulari nterests are molecules that contain multiple CÀHb onds prone to undergo CÀHb ond activations with very similar bond dissociation energies at different positions. This is the case of benzanilides, relevant chemical motifs that are found in many useful fine chemicals, in which two CÀHs ites are present in chemically different aromatic fragments. In the last years, it has been found that depending on the metal catalyst and the reaction conditions, the amide motif might behave as ad irecting group towardst he metal-catalyzed CÀHb ond activation in the benzamide site or in the anilides ite. The impact and the consequences of such subtle control of site-selectivity are herein reviewed with important applicationsi ncarboncarbon and carbon-heteroatomb ond forming processes. The mechanisms unraveling these unique transformations are discussed in order to provide ab etter understanding for future developmentsi nt he field of site-selective CÀHb ond functionalization with transition metal catalysts.

show abstract

“…Later, Prabhu and co-workers reported a counteranion triggered amide-directed C–H vinylation/olefination of benzamides using terminal alkynes (Scheme ). Interestingly, a variety of alkyl/aryl acetylenes and (aryl-alkynyl)silanes reacted smoothly to deliver the ortho -alkenylated products in good yields. The mechanistic studies established the importance of counteranion (e.g., SbF 6 – ) in the desilylation process for vinylation reactions.…”

Section: Amide-directed C–h Bond Functionalizationsmentioning

confidence: 99%

“…Later, Prabhu and co-workers reported a counteranion triggered amide-directed C−H vinylation/olefination of benzamides using terminal alkynes (Scheme 8). 82 Interestingly, a ) in the desilylation process for vinylation reactions. The proposed mechanism for such alkenylation reactions proceeds through 7-membered alkenylated intermediate before it undergoes protodemetalation.…”

Section: T H Imentioning

confidence: 99%

Weak-Coordination in C–H Bond Functionalizations Catalyzed by 3d Metals

2022

View full text Add to dashboard Cite

Transition-metal-catalyzed C–H bond functionalizations have had an enormous influence on organic synthesis in recent times. However, the use of low-abundance 4d and 5d metals is almost inevitable, and they are in high demand. This will be a cause of concern, and hence, it is important to develop methods based on 3d metals, which are widely present in the Earth’s crust. In this regard, the use of 3d metal catalysts or their precursors for catalysis, in general, and C–H bond functionalizations, in particular, has gained significant momentum in the recent times. The major development in catalytic C–H bond functionalizations with 3d metals has been achieved predominantly with strongly coordinating directing groups such as pyridyl, pyrimidinyl, pyrazolyl, and 8-amino-quinolinyl groups. Thus, prefunctionalization of substrates with these directing groups is necessary, which contradicts the step- and atom-economy of C–H bond activation. However, commonly available functional groups such as aldehyde, ketone, carboxylic acid, amide, hydroxy, and N-oxides loosely bind to metals through weak-coordination. These weakly coordinating directing groups orient the metal to activate C–H bond regioselectively without the need for preinstalled strongly coordinating directing groups. Although it is challenging, this contemporary topic has been actively pursued by many researchers in recent times. Through this article, we provide a comprehensive overview of 3d metal-catalyzed, weakly coordinating, directing-group-enabled C–H bond functionalizations reported until March 2021.

show abstract

Cobalt(III)‐Catalyzed C−H Activation: Counter Anion Triggered Desilylative Direct ortho‐Vinylation of Secondary Benzamides

Cited by 17 publications

References 55 publications

Cobalt‐Mediated Decarboxylative/Desilylative C−H Activation/Annulation Reaction: An Efficient Approach to Natural Alkaloids and New Structural Analogues

Cobalt‐Mediated Decarboxylative/Desilylative C−H Activation/Annulation Reaction: An Efficient Approach to Natural Alkaloids and New Structural Analogues

Steering Site‐Selectivity in Transition Metal‐Catalyzed C−H Bond Functionalization: the Challenge of Benzanilides

Weak-Coordination in C–H Bond Functionalizations Catalyzed by 3d Metals

Contact Info

Product

Resources

About